rac-N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamide | 1260236-16-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: rac-N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamide
• CAS: 1260236-16-5；1260236-18-7
• 化学式: C₁₄H₁₆INO
• 分子量: 341.192
• InChiKey: GFOYCCSPQADCKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  rac-N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamide 在 三乙基硼 、 三正丁基氢锡 作用下， 以 正己烷 、 苯 为溶剂， 反应 0.08h， 以10%的产率得到rac-N-(cyclohex-2-enyl)-N-phenylacetamide
  参考文献：
  名称：

  Radical and Heck Cyclizations of Diastereomeric o-Haloanilide Atropisomers

  摘要：

  The outcomes of radical cyclizations and Heck reactions of N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamides depend critically on the configurations of the chiral axis and the stereocenter. In substrates without an or-rho-methyl group, the diastereomeric precursors interconvert slowly at ambient temperatures. Cyclization of enriched mixtures of diastereomers provided similar yields of acetyl tetrahydrocarbazoles or dihydrocarbazoles, suggesting that interconversion of the radical or organometallic intermediates also occurs. Diastereomers of N-(cyclohex-2-enyl)-N-(2-iodo-4,6-dimethylphenyl)acetamides with an additional ortnomethyl group did not interconvert at ambient temperatures and were readily resolved. In radical cyclizations, syn diastereomers were prone to cyclize, while anti isomers were not. Strikingly, Heck reactions gave the opposite result; anti isomers were prone to cyclization and syn isomers were not. Heck reactions of allylic acetates occur with beta-hydride elimination when acetate is trans to palladium and with beta-acetoxy elimination when acetate is cis. This is surprising because prior studies have suggested that a trans relationship of palladium and acetoxy is essential for acetate elimination. Analyses of the results provide insights into mechanisms for radical cyclization and for insertion and elimination in the Heck reaction.

  DOI：

  10.1021/ja108795x
• 作为产物：
  描述：

  3-溴环己烯 在 potassium carbonate 作用下， 以 丙酮 、 乙腈 为溶剂， 反应 36.17h， 生成 rac-N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamide
  参考文献：
  名称：

  Radical and Heck Cyclizations of Diastereomeric o-Haloanilide Atropisomers

  摘要：

  The outcomes of radical cyclizations and Heck reactions of N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamides depend critically on the configurations of the chiral axis and the stereocenter. In substrates without an or-rho-methyl group, the diastereomeric precursors interconvert slowly at ambient temperatures. Cyclization of enriched mixtures of diastereomers provided similar yields of acetyl tetrahydrocarbazoles or dihydrocarbazoles, suggesting that interconversion of the radical or organometallic intermediates also occurs. Diastereomers of N-(cyclohex-2-enyl)-N-(2-iodo-4,6-dimethylphenyl)acetamides with an additional ortnomethyl group did not interconvert at ambient temperatures and were readily resolved. In radical cyclizations, syn diastereomers were prone to cyclize, while anti isomers were not. Strikingly, Heck reactions gave the opposite result; anti isomers were prone to cyclization and syn isomers were not. Heck reactions of allylic acetates occur with beta-hydride elimination when acetate is trans to palladium and with beta-acetoxy elimination when acetate is cis. This is surprising because prior studies have suggested that a trans relationship of palladium and acetoxy is essential for acetate elimination. Analyses of the results provide insights into mechanisms for radical cyclization and for insertion and elimination in the Heck reaction.

  DOI：

  10.1021/ja108795x

文献信息

• Intermolecular oxyarylation of olefins with aryl halides and TEMPOH catalyzed by the phenolate anion under visible light
  作者：Kangjiang Liang、Qian Liu、Lei Shen、Xipan Li、Delian Wei、Liyan Zheng、Chengfeng Xia

  DOI：10.1039/d0sc02160a

  日期：——

  strong reduction potentials. Under visible light irradiation, the phenolate anion enabled the reduction of (hetero)aryl halides (including electron-rich aryl chlorides) to (hetero)aryl radicals through single electron transfer. Based on this new photocatalyst, a novel and efficient photocatalytic protocol for the intermolecular oxyarylation of olefins with aryl halides and TEMPOH was developed. The developed

  酚盐阴离子被发现是一种具有强大还原潜力的新型光催化剂。在可见光照射下，酚酸根阴离子能够通过单电子转移将（杂）芳基卤化物（包括富电子的芳基氯化物）还原为（杂）芳基基团。基于这种新的光催化剂，开发了一种新颖且有效的光催化方案，用于烯烃与芳基卤化物和TEMPOH的分子间氧化。所开发的三组分偶联反应是在氧化还原中性反应条件下，以稳定且易于获得的合成子进行的，并显示了广泛的底物范围。通过对所得的氧化芳基化产物进行多样化的化学处理以及对活性药物成分进行后期修饰，进一步突出了该方法的实用性。